JP2012245668A - Multilayer film-like product and multilayer molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a multilayer film-like product which is excellent in weather resistance and the peelability of a base material film, and to provide a multilayer molded article excellent in weather resistance.SOLUTION: The multilayer film-like product is obtained by layering a cured film of an active energy ray-curable composition containing: the urethane (meth)acrylate (A) which is obtained by at least reacting, on the surface of one side of a polyester film, polydienepolyol (a1) having two or more hydroxyl groups in one molecule thereof, organic polyisocyanate (a2), and a compound (a3) having one or more hydroxyl groups and one or more polymerizable unsaturated double bonds in one molecule thereof, with one another; and a photopolymerization initiator (B). Also, the multilayer molded article is obtained by layering the multilayer film-like product on a molded article.

Description

  The present invention relates to a laminated film-like product having a cured film made of an active energy ray-curable composition, and a laminated molded product obtained by laminating the laminated film-like product on a molded product.

  As a method for decorating a plastic molded product, a method of molding using a thermoplastic resin kneaded with a pigment or the like, and a method of coating with a spray after molding have been common. However, with such a method, it is difficult to meet recent market demands for various design features. Therefore, simultaneous injection molding methods such as transfer foil method, insert molding method and in-mold molding method have come to be used.

  For example, in the transfer foil method, a decorative film-like product having a decorative layer on which a pattern or the like is printed in advance is inserted on the base film, with the base film side facing the mold side, and a thermoplastic resin in the mold Is molded by injection, only the base film is peeled off from the molded product, and the decorative layer is transferred to the surface of the molded product. The injection-molding simultaneous decorating method by the transfer foil method is mainly used for small automotive parts and the like, and in recent years, it is also used for housings such as mobile phones and mobile personal computers.

  The decorative film-like product may be provided with a cured film having hard coat performance for the purpose of imparting scratch resistance to the molded product. The cured film is required to have high surface hardness and stretchability that does not cause cracks even when molded into various shapes. Further, when the molded product is used outdoors, weather resistance is required to maintain the appearance even when exposed to direct sunlight or rain.

  As a material for the cured film, for example, Patent Document 1 proposes an active energy ray-curable composition containing a polyurethane compound obtained from an epoxy (meth) acrylate having two hydroxyl groups in a molecule and a diisocyanate compound.

  However, the active energy ray-curable composition of Patent Document 1 still has room for improvement in the weather resistance of the cured film. Moreover, when using for a transfer foil method, if a peeling layer is not provided in a base film, peelability may not be enough.

JP 2003-212938 A

  An object of the present invention is to provide a laminated film-like product excellent in weather resistance and peelability of a base film, and a laminated molded product excellent in weather resistance.

  The present invention provides a polydiene polyol (a1) having two or more hydroxyl groups in one molecule, an organic polyisocyanate (a2) and one or more hydroxyl groups and one or more hydroxyl groups in one molecule on one surface of a polyester film. Curing of an active energy ray-curable composition comprising a urethane (meth) acrylate (A) obtained by reacting at least a compound (a3) having a polymerizable unsaturated double bond and a photopolymerization initiator (B) It is a laminated film-like product in which films are laminated.

  Furthermore, the present invention is a transfer foil comprising a laminated film-like material further having an adhesive layer on the surface of the cured film of the above-mentioned laminated film-like material or the surface on which the cured film is not laminated.

  Furthermore, the present invention is a laminated molded product in which the laminated film-like product is laminated on the molded product so that the adhesive layer surface of the transfer foil is in contact with the surface of the molded product.

  Furthermore, the present invention is a laminated molded product in which a cured film is transferred to the surface obtained by peeling a polyester film from the laminated molded product.

  ADVANTAGE OF THE INVENTION According to this invention, the laminated film-like thing excellent in the weather resistance and the peelability of a base film, and the laminated molded article excellent in the weather resistance can be provided. This laminated film-like material can be suitably used for, for example, the injection molding simultaneous decorating method as a transfer foil in the transfer foil method. Moreover, this laminated molded product is suitable for use in decorative molded products that require weather resistance, such as automotive parts used outdoors.

[Component (a1)]
The component (a1) used in the present invention is a polydiene polyol having two or more hydroxyl groups in one molecule. By using this component (a1), it is possible to impart excellent weather resistance, stretchability and peelability of the base film to the cured film.

  Specific examples of the component (a1) include polydiene polyols of alkadienes such as butadiene, isoprene, pentadiene, hexadiene and octadiene; polydiene polyols of cyclic dienes such as cyclopentadiene, dicyclopentadiene and ethylidene norbornene; these polydienes Examples thereof include a hydride obtained by hydrogenating a vinylic double bond in the main chain or side chain of a polyol. These can be used alone or in combination of two or more. In particular, from the viewpoint of surface hardness and stretchability of the cured film, polybutadiene polyol, polyisoprene polyol, and one or a combination of two or more of these hydrides are preferable. More preferred is polybutadiene polyol.

  The number average molecular weight of the component (a1) is preferably from 200 to 10,000, and more preferably from 500 to 5,000, from the viewpoint of the surface hardness, weather resistance, and stretchability of the cured film. This number average molecular weight is a molecular weight calculated from a hydroxyl value. The hydroxyl value is calculated according to JIS K1557-1 “Plastic-polyurethane raw material polyol test method”, or the inspection result value of the manufacturer is used. The following formula is used to calculate the number average molecular weight from the hydroxyl value.

  Number average molecular weight = 56.1 × 1000 × 2 / hydroxyl value.

[(A2) component]
The component (a2) used in the present invention is an organic polyisocyanate. By reacting the component (a2) with the hydroxyl group of the component (a1), a tough urethane bond can be introduced into the main chain, and the surface hardness and stretchability of the cured film can be improved.

  Examples of the component (a2) include aromatic diisocyanates such as 2,4′-diphenylmethane diisocyanate; aliphatic diisocyanates; alicyclic diisocyanates such as dicyclohexylmethane-4,4′-diisocyanate; and aromatic aliphatic diisocyanates such as xylene diisocyanate. And these burettes or allophanates. These can be used alone or in combination of two or more. In particular, alicyclic diisocyanates and aliphatic diisocyanates are preferable from the viewpoint of the weather resistance of the cured film, and alicyclic diisocyanates are more preferable from the viewpoint of the surface hardness of the cured film.

  Specific examples of the alicyclic diisocyanate include isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, and methylcyclohexylene diisocyanate. In particular, isophorone diisocyanate and dicyclohexylmethane-4,4′-diisocyanate are preferable from the viewpoint of the surface hardness of the cured film.

[(A3) component]
The component (a3) used in the present invention is a compound having one or more hydroxyl groups and one or more polymerizable unsaturated double bonds in one molecule. By using this component (a3), a polymerizable unsaturated double bond can be introduced at the molecular end of the component (A). The polymerizable unsaturated double bond of the component (a3) is typically an unsaturated double bond of a (meth) acryloyl group. That is, the component (a3) typically has one or more (meth) acryloyl groups. The number of hydroxyl groups is preferably one.

  As the component (a3), for example, mono (meth) acrylate having a hydroxyl group or an alkylene oxide adduct thereof; monohydroxy poly (meth) acrylate or an alkylene oxide adduct thereof; butyl glycidyl ether, 2-ethylhexyl glycidyl ether, glycidyl methacrylate Addition reaction product of a monoepoxy compound such as (meth) acrylic acid; addition reaction product of a polyalkylene glycol such as polyethylene glycol and mono (meth) acrylic acid; a polycaprolactone diol (n = 1-5) mono ( And (meth) acrylate. These can be used alone or in combination of two or more. In particular, from the viewpoint of the surface hardness of the cured film, mono (meth) acrylate and monohydroxypoly (meth) acrylate having a hydroxyl group are preferable. Note that (meth) acrylate means acrylate or methacrylate, and (meth) acrylic acid means acrylic acid or methacrylic acid.

  Specific examples of the mono (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. Specific examples of the monohydroxy poly (meth) acrylate include pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate. In particular, monohydroxy poly (meth) acrylate is preferable from the viewpoint of the surface hardness of the cured film, and pentaerythritol tri (meth) acrylate is more preferable from the viewpoint of compatibility with components other than the component (A) and the surface hardness of the cured film. preferable.

[(A4) component]
The component (a4) used optionally in the present invention is a compound represented by the following formula (1).

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 4.)
By using this component (a4), a functional group is introduced into the side chain, compatibility with components other than the component (A) is improved, and the surface hardness of the cured film can be achieved.

  As the component (a4), glycerol mono (meth) acrylate in which n in the formula (1) is 1 is preferable from the viewpoint of industrial availability.

[(A) component]
Component (A) used in the present invention is urethane (meth) acrylate obtained by reacting at least component (a1), component (a2) and component (a3), preferably component (a1), component (a2) , (A3) component and (a4) component are reacted to obtain urethane (meth) acrylate. This component (A) is a component for imparting excellent surface hardness and stretchability to the cured film.

  The synthesis method of the component (A) is not particularly limited, and a known urethane (meth) acrylate synthesis method can be employed. For example, there is a method of obtaining the component (A) by sequentially dropping the component (a2) and then the component (a3) into a mixture of the component (a1) and the polyurethane catalyst. The reaction temperature at that time is preferably about 50 to 90 ° C.

  Examples of the polyurethane forming catalyst include amine-based catalysts and organometallic catalysts. Specific examples of the amine catalyst include triethylamine, N, N-dimethylcyclohexylamine, and dimethanolamine. These can be used alone or in combination of two or more. Specific examples of organometallic catalysts include stannous octoate, stannous laurate, di-n-butyltin dilaurate, di-n-butyltin dimaleate, di-n-butyltin diacetate, and di-n-octyl. Organic tin compounds such as tin diacetate can be mentioned. These can be used alone or in combination of two or more. In particular, an organometallic catalyst is preferable, and di-n-butyltin dilaurate is more preferable because a high catalytic effect can be obtained with a small amount.

  When obtaining the component (A), the temperature control during the synthesis of the component (A) is facilitated, the viscosity of the obtained component (A) is reduced, and the workability is improved. At least one selected from components a1) to (a4) can be used by diluting in a diluent solvent for component (A). Examples of the diluent solvent for component (A) include aromatic solvents such as toluene and xylene; cyclic hydrocarbon solvents such as cyclohexane; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ethyl acetate and n-butyl acetate. Acetate solvent These can be used alone or in combination of two or more.

  The end point of the reaction for obtaining the component (A) can be confirmed by the residual amount of isocyanate groups in the obtained component (A).

(A) As a residual amount of the isocyanate group in a component, 0.05 mol% or less is preferable and 0.01 mol% or less is more preferable. The remaining amount of the isocyanate group is a value determined by a back titration method using amine and hydrochloric acid. A specific method for quantifying isocyanate groups is as follows.
(1) The component (A) (W [g]) is dissolved in 25 ml of a solvent such as chlorobenzene and further mixed with 25 ml of a 0.1N di-n-butylamine chlorobenzene solution.
(2) Add 1 to 2 drops of a commercially available indicator such as bromophenol blue to the resulting mixture and titrate with a commercially available 0.1N hydrochloric acid ethanol solution.
(3) When the mixed solution turns from blue purple to yellow, the end point is set, and the dripping amount (Y [ml]) is read.
(4) The same operation is performed without the component (A) to obtain a blank dripping amount (X [ml]).
(5) The residual amount of isocyanate groups is calculated using the following formula.
(Remaining amount of isocyanate group [%]) = (Y−X) × F × 0.42 / W
X: A drop amount of 0.1N hydrochloric acid ethanol solution [ml] for the sample of component (A),
Y: dripping amount of 0.1N hydrochloric acid ethanol solution with respect to blank [ml],
F: Factor value of 0.1N hydrochloric acid ethanol solution,
W: Mass of component (A) [g].

  The weight average molecular weight (Mw) of the component (A) is preferably 1,000 to 100,000, more preferably 1,500 to 30,000. When Mw is within these ranges, the component (A) can be stably produced without gelation, and the workability of the component (A) itself and the stretchability of the cured film are also improved.

  For this Mw, a tetrahydrofuran solution (0.4% by mass) of an active energy ray-curable composition was prepared, and columns manufactured by Tosoh Corporation (TSK Gel Super HZM-M and TSK Guard Column Super HZ-L, trade name) 100 μl of the above solution was injected into a gel permeation chromatography apparatus (HLC-8320GPC EcoSEC, trade name) manufactured by Tosoh Corporation, equipped with a sample, and measured under conditions of a flow rate of 1 ml / min, an eluent tetrahydrofuran, and a column temperature of 40 ° C. It is a value converted with standard polystyrene.

  Mw of (A) component can be adjusted with the molar ratio of (a1) component-(a4) component. The molar ratio is preferably such that M represented by the following formula is 1.0 or more and less than 1.2.

M = [(m ₁ + m ₄ ) × 2 + m ₃ ] / (m ₂ × 2)
[M ₁ , m ₂ , m ₃ and m ₄ represent the molar amounts of the component (a1), the component (a2), the component (a3) and the component (a4), respectively, and (m ₁ + m ₄ ) = m ₂ − 1. ]
By setting M within the above range, more preferably M = 1, the viscosity of the component (A) can be lowered, and the surface hardness and stretchability of the cured film can be improved.

[Component (B)]
Component (B) is a photopolymerization initiator and is a component for efficiently curing the composition with active energy rays.

  Examples of the component (B) include acetophenone compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, and acylphosphine oxide compounds. These can be used alone or in combination of two or more. In particular, from the viewpoint of curability of the composition, surface hardness of the cured film and scratch resistance, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl-phenyl ketone, 2, 4, 6 A group consisting of trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one At least one photopolymerization initiator selected from the above is preferred.

[Active energy ray-curable composition]
The active energy ray-curable composition used in the present invention is a composition comprising the component (A) and the component (B) described above.

  In the active energy ray-curable composition, (meth) acrylate (C) other than the component (A) can be blended for the purpose of imparting surface hardness to the cured film. Examples of the component (C) include mono (meth) acrylate, di (meth) acrylate, trifunctional or higher polyfunctional (meth) acrylate, epoxy poly (meth) acrylate, urethane poly (meth) acrylate, polyester poly ( And (meth) acrylate.

  Specific examples of mono (meth) acrylates include alkyl mono (meth) acrylates having a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and linear, branched or cyclic having 1 to 20 carbon atoms. Examples include hydroxyalkyl mono (meth) acrylates having a hydroxyalkyl group of structure.

  Specific examples of di (meth) acrylate include linear, branched or ring structures such as 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, dicyclopentanediol di (meth) acrylate Di (meth) acrylates of alkanediols having the above and their alkylene oxide adducts; polyether diol di (meth) acrylates such as polyethylene glycol (repeating units n = 2 to 15) di (meth) acrylates.

  Specific examples of trifunctional or higher polyfunctional (meth) acrylates include (meth) acrylic acid modified products of polyhydric alcohols such as trimethylolpropane, pentaerythritol, and glycerin and alkylene oxide modified products thereof; tris (2-hydroxyethyl) ) Isocyanurate modified with (meth) acrylic acid and its modified alkylene oxide.

  Specific examples of the epoxy poly (meth) acrylate include bisphenol type epoxy di (meth) acrylate obtained by reacting a bisphenol type epoxy resin obtained by a condensation reaction of bisphenol A and epichlorohydrin with (meth) acrylic acid.

  Specific examples of the urethane poly (meth) acrylate include a hydroxy group-containing (meth) acrylate having at least one organic isocyanate compound, one or more (meth) acryloyloxy groups and one hydroxy group in the molecule, and Examples thereof include compounds obtained by reacting at least one diol selected from alkane diol, polyether diol, polybutadiene diol, polyester diol, polycarbonate diol, and amide diol as necessary.

  Specific examples of the polyester poly (meth) acrylate include compounds obtained by a reaction between a polybasic acid such as phthalic acid, a polyhydric alcohol such as ethylene glycol, and (meth) acrylic acid.

  Each of the above components (C) can be used alone or in combination of two or more.

  As the component (C), a trifunctional or higher polyfunctional (meth) acrylate is particularly preferable from the viewpoint of the surface hardness of the cured film. Specific examples of preferable trifunctional or higher polyfunctional (meth) acrylates include trimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tri (meth). Examples include acrylate, pentaerythritol tetra (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, and bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate. Among them, at least one trifunctional or more functional group selected from the group consisting of dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate Polyfunctional (meth) acrylate is more preferable.

  The blending amount of the component (A) in the active energy ray-curable composition is preferably 10 to 95 parts by weight, more preferably 20 to 90 parts by weight, in a total of 100 parts by weight of the component (A) and the component (C). . If the blending amount of component (A) is within these ranges, the workability of the composition will be good, and a cured film excellent in surface hardness, stretchability and weather resistance will tend to be obtained.

  The blending amount of the component (B) in the active energy ray-curable composition is preferably 0.01 to 50 parts by weight, and 0.1 to 100 parts by weight in total of the components (A) and (C). 30 parts by mass is more preferable. If the blending amount of component (B) is within these ranges, the curability of the composition will be good, and a cured film excellent in surface hardness and scratch resistance will tend to be obtained.

  The blending amount of the component (C) in the active energy ray-curable composition is preferably 5 to 90 parts by mass, more preferably 10 to 80 parts by mass, in a total of 100 parts by mass of the component (A) and the component (C). . If the blending amount of component (C) is within these ranges, the workability of the composition will be good, and a cured film excellent in surface hardness, stretchability and weather resistance will tend to be obtained.

  A polymerization inhibitor can be mix | blended with an active energy ray curable composition as needed. Specific examples of the polymerization inhibitor include nitroso polymerization inhibitors such as nitrosophenylhydroxylamine ammonium salt; quinone polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether and benzoquinone; N, N-diphenylpicrylhydrazyl (DPPH) And radical scavengers such as triphenylmethyl; and benzotriazole antioxidants. These can be used alone or in combination of two or more.

  For active energy ray-curable compositions, non-reactive thermoplastic polymer compounds, organic bentons, polyamides, microgels, rheology modifiers such as fiber-based resins, surface modifiers such as silicone, UV absorption Various additives such as an agent, a light stabilizer, an antioxidant, a polymerization inhibitor, a silane coupling agent, an organic filler, and an anti-sagging agent can be blended.

  In the active energy ray-curable composition, an inorganic filler can be blended as necessary for the purpose of imparting scratch resistance, shape stability, heat resistance or slipperiness of the cured film, or improving conductivity. As a method for blending the inorganic filler, a known method can be adopted.

  For the purpose of imparting shape stability, heat resistance, and slipperiness of the cured film, examples of the inorganic filler include metal oxides such as silica, alumina, and titanium oxide, or composite oxides thereof, and metal oxides thereof. Alternatively, a surface-treated metal oxide or surface-treated composite oxide obtained by coating the surface of the composite oxide with a silane coupling agent or the like, or a hydroxide such as aluminum hydroxide, magnesium hydroxide, or potassium hydroxide can be used.

  For the purpose of improving the conductivity of the cured film, as the inorganic filler, for example, metal particles such as gold, silver, copper, nickel or alloys thereof, conductive particles such as carbon, carbon nanotube, carbon nanohorn, fullerene, Particles obtained by coating a metal or ITO (indium tin oxide) on the surface of glass, ceramic, plastic, metal oxide or the like can be used. In particular, from the viewpoint of conductivity, particles having an aspect ratio (major axis / minor axis) of 5 or more are preferable.

  The inorganic filler is preferably particles having an area average particle diameter of 1 μm or less from the viewpoint of the optical performance of the composition.

  What is necessary is just to adjust the compounding quantity of an inorganic filler suitably according to the use of an active energy ray curable composition, the required mechanical strength, fluidity | liquidity, etc.

  When apply | coating an active energy ray curable composition to the surface of a base material, it can dilute with an organic solvent as needed for the purpose of adjusting a viscosity according to the application | coating method. Specific examples of the organic solvent include alcohol solvents such as methyl alcohol, ethyl alcohol and isopropyl alcohol; ether solvents such as propylene glycol monomethyl ether, and the same solvent as the dilution solvent for component (A) described above. . From the viewpoint of coating workability, the amount of the organic solvent is preferably 20% by mass or more of the final composition when the curable component in the composition is applied. For example, when the composition is spray-coated, it is usually preferable to add an organic solvent using a Ford Cup No. 4 viscometer so as to have a viscosity of about 15 to 60 seconds at 20 ° C.

[Laminated film]
The laminated film-like product of the present invention is formed by laminating a cured film of the active energy ray-curable composition described above on one surface of a polyester film.

  Since the base film is a polyester film, the laminated film-like product is excellent in stretchability of the laminated film-like product, and is excellent in economy from the viewpoint of production cost and the like. Moreover, since this laminated film-like product has a cured film having excellent surface hardness, it is useful as a hard coat film provided on the surface of a molded product. Moreover, since it is excellent also in a drawability, it is useful also as the transfer foil etc. which are used for the in-mold decoration method at the time of injection molding.

  Various additives such as an antioxidant, a light stabilizer, an ultraviolet absorber, a fluorescent whitening agent, a transesterification agent, and an antistatic agent can be blended in the polyester resin constituting the polyester film, if necessary. The surface of the polyester film may further be provided with a decorative layer, an easy-adhesion layer or a release layer to which a design such as a pattern is given according to the purpose.

  The thickness of the polyester film is preferably 0.05 to 1 mm from the viewpoint of the surface hardness of the laminated film, and more preferably 0.05 to 0.2 mm from the viewpoint of the moldability of the laminated film. The thickness of the cured film is preferably from 0.001 to 0.1 mm from the viewpoint of the curability of the composition and the surface hardness of the laminated film, and from the viewpoint of the moldability of the laminated film. 01 mm is preferred.

  The laminated film can be formed, for example, by applying an active energy ray-curable composition on one surface of a polyester film and curing it by irradiation with active energy rays.

  Examples of the method for applying the active energy ray-curable composition include a bar coater coating method, a Mayer bar coating method, an air knife coating method, a gravure coating method, a reverse gravure coating method, a micro gravure coating method, a brush coating method, and a spray coating. Method, shower flow coating method, dip coating method, curtain coating method, offset printing method, flexographic printing method, screen printing method, and potting method.

  Examples of active energy rays used for curing include α rays, β rays, γ rays, and ultraviolet rays. From the viewpoint of versatility, ultraviolet rays are preferable. Examples of the ultraviolet ray generation source include a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a metal halide lamp, an electrodeless UV lamp using a magnetron, and an LED.

  The atmosphere for curing may be air or an inert gas such as nitrogen or argon. Air is preferable in terms of practicality and economy.

As curing conditions, for example, when ultraviolet rays are used as active energy rays, it is preferable to use a high-pressure mercury lamp to irradiate so that the integrated light amount is about 300 mJ / cm ² .

  When manufacturing a molded product having a laminated film-like material laminated on the surface, an adhesive layer is applied to the surface of the laminated film-like product that is in contact with the molded product surface (the surface of the cured film or the surface on which the cured film is not laminated). It is preferable to have.

  As the adhesive layer, a thermoplastic resin or a curable resin is used depending on the type of resin constituting the molded product. Examples of the thermoplastic resin include acrylic resin, thermoplastic urethane resin, thermoplastic polyester resin, and polyamide resin. Examples of the thermosetting resin include a urethane resin in which an acrylic, polyester, or polyether polyol is thermoset with an isocyanate crosslinking agent. As the isocyanate-based crosslinking agent, polyisocyanates such as the above-mentioned isocyanate monomers and their trimers are used as specific examples of the component (a2). An adhesive layer is obtained by coating these resins by a known means and drying or drying and curing the resins. The thickness of the adhesive layer is preferably 0.1 to 5 μm.

  When using a laminated film-like material as a decorative film, a decorative layer such as a printed layer can be provided on the surface of one side of the polyester film (the side on which the cured film is not laminated). In this case, an adhesive layer can also be formed on the decorative layer of the laminated film.

[Laminated molded products]
The laminated molded product of the present invention is formed by laminating a laminated film product on the molded product so that the adhesive layer surface of the laminated film product described above and the surface of the molded product are in contact with each other.

  Examples of the resin constituting the molded article include thermoplastic resins such as acrylic resin, polycarbonate resin, acrylonitrile-butadiene-styrene copolymer (ABS resin), polymer alloy containing polycarbonate resin, and polyester resin. In addition, this resin includes antioxidants, light stabilizers, ultraviolet absorbers, lubricants, plasticizers, stabilizers, mold release agents, antistatic agents, colorants, flame retardants, glass fibers, carbon fibers as necessary. Various additives such as anti-drip agents can be blended.

  For example, when using a laminated film with an adhesive layer on the surface where the cured film is not laminated, the polyester film side adheres to the molded product and the cured film becomes the surface layer. What is necessary is just to use as it is as a laminated molded object with a film. The resin constituting the molded product in this case is preferably a thermoplastic resin that can be fused and integrated with the polyester film, and particularly preferably a polyester resin.

  On the other hand, when using the laminated film-like material provided with the adhesive layer on the surface of the cured film as the transfer foil, the cured film adheres to the molded product, and the polyester film becomes the surface side. If the polyester film is peeled from such a laminated molded product, only the cured film is transferred to the molded product surface. In this case, in order to facilitate peeling, a peeling layer can be provided between the polyester film of the film-like material and the cured film. As the release layer, for example, a composition prepared by dissolving or dispersing a release agent such as waxes, fluorine resin, or silicon resin with a desired additive dissolved in a solvent is applied and dried. It is obtained by. The thickness of the release layer is preferably from 0.1 to 5 μm.

  In any of the above laminated molded products, the scratch resistance and weather resistance are improved by the cured film on the surface. Moreover, if the laminated film-like thing which further has decorating layers, such as a printing layer, is used, it can respond to the request | requirement of the market which asks for various design properties.

  As a method for producing a laminated molded product, for example, when a resin material is injection-molded, a laminated film-like product is first mounted on the mold surface, and then injection-molded to form a laminated film-like material on the surface of the molded product. The method of laminating objects, the so-called injection molding simultaneous decoration method is preferred. Specifically, an insert molding method, an in-mold lamination method, and an in-mold decoration method (transfer foil method) can be applied.

  Hereinafter, the present invention will be described with reference to examples. In the following description, “part” means “part by mass” and “%” means “% by mass”. The evaluation method is as follows.

(1) Weather resistance:
For the laminated film-like material, using a sunshine carbon weatherometer WEL-SUN-HC-B type weather resistance tester manufactured by Suga Test Instruments Co., Ltd., black panel temperature 63 ± 3 ° C., rainfall 12 minutes, irradiation 48 minutes A total of 100 hours of weather resistance tests were conducted under the cycle conditions. The surface state of the cured film side of the film-like product after the test was observed with a polarizing microscope Eclipse LV100 (100 times magnification) manufactured by Nikon Instruments Co., Ltd., and a defect (fish eye shape) in a unit area (1 mm × 1 mm) The number of round defects) was confirmed, and the weather resistance was determined according to the following criteria.
“O”: No defect.
“X”: There are one or more defects.

(2) Peelability:
About the laminated molded product, the base film (PET film) was peeled by hand, and the peelability was determined according to the following criteria depending on whether the cured film remained on the peeled base film side.
“◯”: A cured film did not remain on the peeled substrate film side.
“X”: A cured film remained on the peeled substrate film side.

[Synthesis Example 1: Synthesis of component (A)]
In a reaction vessel equipped with a flask, a stirrer, a temperature controller and a condenser, 486.9 parts of toluene, polybutadiene glycol (manufactured by Nippon Soda Co., Ltd., trade name: NISSO PB G-1000, number average molecular weight determined from hydroxyl value = 1524) 410 parts, dicyclohexylmethane-4,4′-diisocyanate (manufactured by Sumitomo Bayer Co., Ltd., trade name Desmodur W), 265 parts, hydroquinone monomethyl ether 0.3 part, charged to 60 ° C. with stirring. 0.2 parts of di-n-butyltin dilaurate was added. Then, 32 parts of glycerin monomethacrylate (Nippon Yushi Co., Ltd., trade name Blemmer GLM) was added dropwise over 1 hour. Thereafter, stirring was continued for 3 hours. Subsequently, 428.8 parts of pentaerythritol triacrylate (manufactured by Toa Gosei Co., Ltd., trade name Aronix M-306) was added dropwise over 2 hours. Thereafter, the temperature was raised to 70 ° C. over 1 hour, and stirring was further continued for 5 hours to obtain urethane acrylate (NU-1) as the component (A).

  The urethane acrylate (NU-1) had a weight average molecular weight (Mw) of 8,600 and was transparent in appearance. The evaluation results are shown in Table 1.

[Synthesis Examples 2 and 3: Synthesis of Component (A)]
(A) Urethane acrylates (NU-2) and (NU-3) as components (A) in the same manner as in Synthesis Example 1 except that the type and blending amount of the raw materials are changed as shown in Table 1. Got. The evaluation results are shown in Table 1.

Abbreviations in Table 1 indicate the following compounds: “PBG1”: polybutadiene glycol (manufactured by Nippon Soda Co., Ltd., trade name NISSO PB G-1000, number average molecular weight determined from hydroxyl value = 1524),
"PBG2": polybutadiene glycol (manufactured by Nippon Soda Co., Ltd., trade name NISSO PB G-2000, number average molecular weight determined from hydroxyl value = 2166),
“H-MDI”: dicyclohexylmethane-4,4′-diisocyanate (manufactured by Sumitomo Bayer Co., Ltd., trade name Desmodur W, molecular weight determined from structural formula = 264.8),
“PETA”: pentaerythritol triacrylate (manufactured by Toagosei Co., Ltd., trade name Aronix M-306, number average molecular weight determined from hydroxyl value = 357.3),
"GLM": glycerin monomethacrylate (manufactured by NOF Corporation, trade name Blemmer GLM, molecular weight determined from structural formula = 160),
"DBTDL": di-n-butyltin dilaurate,
"MEHQ": Hydroquinone monomethyl ether.

[Synthesis Example 4: Synthesis of Component (C)]
In a 5 liter four-necked flask, 346 parts of bisphenol A diepoxy resin (manufactured by Toto Kasei Co., Ltd., trade name Epototo YD8125), 144 parts of acrylic acid (manufactured by Mitsubishi Chemical Corporation, trade name: 100% acrylic acid), Add 0.5 parts of hydroquinone monomethyl ether as a polymerization inhibitor and 2.5 parts of dimethylaminoethyl methacrylate (trade name Acryester DM, manufactured by Mitsubishi Rayon Co., Ltd.) as a catalyst. The reaction was continued for 14 hours while maintaining at 95 ° C. When the acid value of the liquid in the flask became 1 mgKOH / g or less, the first-stage reaction was terminated to produce an epoxy acrylate having two hydroxyl groups in the molecule. Next, the temperature inside the flask was lowered to 60 ° C., 705 parts of ethyl acetate as an organic solvent was added, 0.11 part of di-n-butyltin dilaurate was added as a polyurethane-forming catalyst, and dicyclohexylmethane diisocyanate ( 212 parts of Sumika Bayer Urethane Co., Ltd., trade name Death Module W) was added dropwise over 2 hours. Reaction was continued for 5 hours after completion | finish of dripping of dicyclohexylmethane diisocyanate, and the urethane compound (EP-1) (solid content 50%) of Mw15000 was obtained.

[Example 1]
As component (A), 142.9 parts of urethane acrylate compound (NU-1) obtained in Synthesis Example 1, and as component (B), 1 part of 1-hydroxycyclohexyl phenyl ketone (trade name: Irgacure 184, manufactured by BASF Japan Ltd.) Then, 190.4 parts of ethyl acetate was blended as an organic solvent to obtain an active energy ray-curable composition having a solid content concentration of 30%.

This active energy ray-curable composition is coated on an easy-adhesion treated surface of an easy-adhesion-treated polyethylene terephthalate film (trade name Cosmo Shine A4100, thickness 0.188 mm, manufactured by Toyobo Co., Ltd.) using a bar coater # 10. did. Next, the coated film was dried by heating with a hot air dryer at 100 ° C. for 30 seconds. After that, using a high-pressure mercury lamp, an ultraviolet ray with an integrated light amount of 300 mJ / cm ² (an ultraviolet integrated energy amount of a wavelength of 320 to 380 nm) is irradiated to cure the coating film, and a smooth cured film having a thickness of 3 μm (= 0.003 mm). A laminated film-like product (i) having

  When the weather resistance test was conducted on this laminated film-like material (I), no defects were generated, and it was confirmed that the weather resistance was excellent. The evaluation results are shown in Table 2.

  Also, the thickness of the active energy ray-curable composition was 3 μm in the same manner as the laminated film-like material (A) except that the active energy ray-curable composition was coated not on the easy-adhesion-treated surface of the easy-adhesion-treated polyethylene terephthalate film but on the untreated surface side. A laminated film having a smooth cured film was obtained. A hydroxyl group-containing acrylic resin (manufactured by Mitsubishi Rayon Co., Ltd., trade name: Dianal LR-254, hydroxyl value: 100 mgKOH / g, solid content: 50% by weight) 112 as a main component of the adhesive layer is formed on the cured film of the laminated film. Part, 16.8 parts of polyisocyanate (trade name Coronate HX, manufactured by Nippon Polyurethane Co., Ltd.), 0.02 part of di-n-butyltin dilaurate, and 114 parts of ethyl acetate as a solvent. Was painted using a bar coater # 3. Thereafter, it was heated and dried for 5 minutes with a hot air dryer at 100 ° C. to obtain a laminated film (B) having an adhesive layer having a thickness of 1 μm (= 0.001 mm) on the cured film.

  This laminated film-like material (B) was superposed on a 1 mm thick polymethacrylic plate (trade name Acrylite L, manufactured by Mitsubishi Rayon Co., Ltd.) so that the adhesive layer surface was in contact. Then, using a vacuum heating press IMC-11FA manufactured by Imoto Seisakusho, vacuum bonding was performed under conditions of a temperature of 100 ° C. and a load of 18.6 MPa (= 3000 kg) to obtain a laminated molded product.

  When the peelability of the PET film was evaluated for this laminated molded product, no cured film remained on the peeled substrate film side, and it was confirmed that the peelability was excellent. The evaluation results are shown in Table 2.

[Examples 2 to 4 and Comparative Example 1]
A laminated film product and a laminated molded article were obtained in the same manner as in Example 1 except that the composition of the active energy ray-curable composition was changed as shown in Table 2. The evaluation results are shown in Table 2.

The numerical values in parentheses for the components (A) and (C) in Table 2 indicate the solid content (parts). Moreover, the symbol in Table 2 shows the following compounds.
"NU-1": urethane acrylate compound obtained in Synthesis Example 1
"NU-2": urethane acrylate compound obtained in Synthesis Example 2,
"NU-3": urethane acrylate compound obtained in Synthesis Example 3,
"IT-1": 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF Japan Ltd., trade name Irgacure 184),
“PETA”: pentaerythritol triacrylate (manufactured by Toa Gosei Co., Ltd., trade name Aronix M-306),
"EP-1": polyurethane compound obtained in Synthesis Example 4
"EA": ethyl acetate.

  From the evaluation results of Examples 1 to 4 in Table 2, it can be seen that the cured film of the laminated film of the present invention is excellent in weather resistance and excellent in peelability. In addition, although the laminated molded product of each Example was manufactured by press molding, it can be understood from the above excellent results that the same result can be obtained even when manufactured by the simultaneous injection molding method such as the transfer foil method. .

  On the other hand, in Comparative Example 1, from the urethane acrylate compound not corresponding to the component (A) in the present invention, that is, from the epoxy (meth) acrylate having two hydroxyl groups in the molecule as described in Patent Document 1, and the diisocyanate compound. Since the obtained polyurethane compound was used, the weather resistance and peelability were inferior compared with Examples 1-4.

Claims (7)

  Polydiene polyol (a1), organic polyisocyanate (a2) having two or more hydroxyl groups in one molecule and one or more hydroxyl groups and one or more polymerizable unsaturated groups in one molecule on one surface of the polyester film A cured film of an active energy ray-curable composition comprising a urethane (meth) acrylate (A) obtained by reacting at least a compound having a double bond (a3) and a photopolymerization initiator (B) is laminated. Laminated film. Urethane (meth) acrylate (A) has (a1) component, (a2) component, (a3) component and the following formula (1)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 4.)
The laminated film-like product according to claim 1, which is a urethane (meth) acrylate obtained by reacting the compound (a4) represented by formula (1).   A transfer foil comprising a laminated film-like material further having an adhesive layer on the cured film surface of the laminated film-like material according to claim 1 or 2.   A laminated molded product in which the laminated film-like product is laminated on the molded product such that the adhesive layer surface of the transfer foil according to claim 3 is in contact with the surface of the molded product.   A laminated molded product having a cured film transferred to a surface obtained by peeling a polyester film from the laminated molded product according to claim 4.   A laminated film-like product having an adhesive layer on the surface on which the cured film of the laminated film-like product according to claim 1 or 2 is not laminated.   A laminated molded product in which the laminated film-like product is laminated on the molded product so that the adhesive layer surface of the laminated film-like product according to claim 6 and the surface of the molded product are in contact with each other.